JP5959514B2 - Low surface energy substrate coating method - Google Patents

Description

  The present invention relates to a method of coating a low surface energy substrate. The invention also relates to the novel polymers obtained there.

  The present invention desirably provides a convenient method of coating a variety of low surface energy substrates, including polyolefins and other polymer substrates. The present invention can adhere to low surface energy substrates and can act as a receiver for further coatings, or as a substrate suitable for finishing, or as a layer that allows for sufficient adhesion. It is desirable to provide a coating. However, to date, no such coatings existed.

  The present invention, in at least some embodiments, solves the above problems and meets the above needs.

According to a first aspect of the invention, there is provided a method of coating a low surface energy substrate, the method comprising:
Formula (I)
Wherein R ¹ is i) CR ^a , where R ^a is hydrogen or alkyl, ii) S (O) _p R ¹³ , or SiR ¹⁴ , where R ¹³ and R ¹⁴ are Each independently selected from hydrogen or hydrocarbyl, p is 0, 1 or 2, q is 1 or 2, and iii) C (O) N, S (O) ₂ N, C ( O) ON, CH ₂ ON or CH = CHR ^c N, where R ^c is an electron withdrawing group, or iv) OC (O) CH, C (O) OCH or S (O) ₂ CH Wherein R ¹² is hydrogen, halo, nitro, hydrocarbyl, optionally substituted or interposed with a functional group, or
Is;
R ² and R ³ are each independently selected from the group (CR ⁷ R ⁸ ) _n or CR ⁹ R ¹⁰ , CR ⁷ R ⁸ CR ⁹ R ¹⁰ or CR ⁹ R ¹⁰ CR ⁷ R ⁸ , wherein , N is 0, 1 or 2, R ⁷ and R ⁸ are each independently selected from hydrogen or alkyl, either R ⁹ or R ¹⁰ is hydrogen, and the other is Are electron withdrawing groups, or R ⁹ and R ¹⁰ together form an electron withdrawing group;
R ⁴ and R ⁵ are each independently selected from CH or CR ¹¹ , where CR ¹¹ is an electron withdrawing group;
The dotted line indicates the presence or absence of a bond, and X ¹ is a CX ² X ³ group. In this case, there is no destination to which the dotted bond is bonded, and this is a CX ² group. , The destination of the dotted bond is present, Y ¹ is a CY ² Y ³ group, in which case the destination of the dotted line is not present and is a CY ² group, The destination of the dotted bond is present, X ² , X ³ , Y ² and Y ³ are each independently selected from hydrogen, fluorine or other substituents),
Providing a polymer precursor comprising:
Step a); and
(I) coating the low surface energy substrate with the polymer precursor and polymerizing the polymer precursor to form a polymer coating, or
(Ii) polymerizing the polymer precursor, contacting the polymerized polymer precursor with the low surface energy substrate to form a polymer coating on the low surface energy substrate;
One of the
Step b)
including.

  Thus, a low surface energy substrate such as polypropylene can be coated. While not wishing to be bound by any particular theory, at least some of the problems with bonding to low surface energy substrates are primarily that the deposited layer has a surface tension that is lower than the surface energy surface tension of the substrate. It is necessary. It is sufficiently hydrophobic in nature or otherwise suitable for adhering to low surface energy substrates, but nevertheless double bonds or bonds are sufficiently active with respect to possible polymerization A compound of formula (I) can be provided which can be

  For the avoidance of doubt, the term “polymer precursor” is meant to refer to monomers and prepolymers obtained by partial or semi-polymerization of one or more monomers.

Preferably, R ¹⁶ is a C ³ -C ¹² alkyl group, most preferably a C ⁵ -C ⁸ alkyl group.

  Preferably, the polymer precursor is polymerized by exposure to ultraviolet radiation. An alternative polymerization method is to heat in the presence of an initiator, optionally by application of other types of initiators such as chemical initiators, or by initiation with an electron beam (IR irradiation type and Can also be included). The expression “chemical initiator” as used herein initiates polymerization, such as free radical initiators and ionic initiators such as cationic or anionic initiators, well known in the art. Refers to a compound that can. Polymerization induced by irradiation or electron beam is sufficiently effective even in the substantial absence of solvent. As used herein, the expression “substantially in the absence of solvent” means that a small amount of diluent may be present to allow the reagent to flow but the absence of solvent or complete dissolution of the reagent. Which means that there is not enough solvent to do.

In a preferred embodiment, the polymer precursor is polymerized by exposure to ultraviolet radiation, and the polymerization occurs either spontaneously or in the presence of a suitable initiator. Examples of suitable initiators include 2,2′-azobisisobutyronitrile (AIBN); benzophenones, especially aromatic ketones such as acetophenone; chlorinated acetophenones such as di- or tri-chloroacetophenone; dimethoxyacetophenone ( Dialkoxyacetophenone such as the product name “Irgacure 651”; dialkylhydroxyacetophenone such as dimethylhydroxyacetophenone (commercial product “Darocure 1173”);
Wherein R ^y is alkyl, in particular 2,2-dimethylethyl, R ^x is halogen such as hydroxyl or chloro, and R ^p and R ^q are each independently alkyl or chloro, etc. Selected from halogens (examples are commercial products of the product names "Darocur 1116" and "Trigonal P1")
1-benzoylcyclohexanol-2 (commercial product of “Irgacure 184”); derivatives of benzoin or benzoin acetate, especially benzoin alkyl ethers such as benzoin butyl ether; Dialkoxybenzoin such as benzoin or deoxybenzoin; dibenzylketone; acyl oxime methyl or ethyl ester of oxime (commercial product of “Quantaque PDO”); acyl phosphine oxide; dialkyl acyl phosphonate For example, the following formula
(Wherein Rz is alkyl and Ar is an aryl group)
Silfosphonates such as ketosulfides; dibenzoyl disulfides such as 4,4′-dialkylbenzoyl disulfides; diphenyldithiocarbonates; benzophenones; 4,4′-bis (N, N-dialkylamino) benzophenones; fluorenones; Benzyl; or
(In the formula, Ar is an aryl group such as phenyl, and Rz is an alkyl such as methyl (a commercial product of the product name “Speedcure BMDS”)).
Is mentioned.

  As used herein, the term “alkyl” refers to a straight or branched alkyl group, preferably containing 20 or fewer, more preferably 6 or fewer carbon atoms. The terms “alkenyl” and “alkynyl” refer to unsaturated straight or branched chains and include, for example, 2 to 20 carbon atoms, such as 2 to 6 carbon atoms. Each chain may contain one or more double to triple bonds. Furthermore, the term “aryl” refers to an aromatic group such as phenyl or naphthyl.

  As used herein, the term “hydrocarbyl” refers to any structure containing carbon and hydrogen atoms. For example, they may be aryl such as alkyl, alkenyl, alkynyl, phenyl or naphthyl, arylalkyl, cycloalkyl, cycloalkenyl or cycloalkynyl. Preferably they contain no more than 20, preferably no more than 10 carbon atoms. The term “heterocyclyl” is aromatic or non-cyclic having, for example, 4-20, preferably 5-10 ring atoms, at least one of which is a heteroatom such as oxygen, sulfur, nitrogen, etc. Includes aromatic rings. Examples of such groups are furyl, thienyl, pyrrolyl, pyrrolidinyl, imidazolyl, triazolyl, thiazolyl, tetrazolyl, oxazolyl, isoxazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, benzthiazolyl, Oxazolyl, benzothienyl or benzofuryl is included.

The term “functional group” is, for example, halo, cyano, nitro, oxo, C (O) _n R ^a , OR ^a , S (O) _t R ^a , NR ^b R ^c , OC (O) NR ^b R ^c , C (O) NR ^b R ^c , OC (O) NR ^b R ^c , -NR ⁷ C (O) _n R ⁶ , -NR ^a CONR ^b R ^c , -C = NOR ^a , -N = CR ^b R ^c , S (O) _t NR ^b R ^c , C (S) _n R ^a , C (S) OR ^a , C (S) NR ^b R ^c, or —NR ^b S (O) _t R ^a , R ^a , R ^b and R ^c are each independently selected from hydrogen or an optionally substituted hydrocarbyl group, or R ^b and R ^c are both further heterogeneous such as S (O) _s , oxygen, nitrogen, etc. Forms an optionally substituted ring optionally containing atoms, n is an integer of 1 or 2, t is 0 or 1 to 1 A reactive group such as an integer of 3. In particular, the functional groups are halo, cyano, nitro, oxo, C (O) _n R ^a , OR ^a , S (O) _t R ^a , NR ^b R ^g , OC (O) NR ^b R ^c , C (O ^{) NR b R c, OC (} O) NR b R c, -NR 7 C (O) n R 6, -NR a CONR b R c, -NR a CSNR b R c, -C = NOR a, -N = CR ^b R ^c , S (O) _t NR ^b R ^c or —NR ^b S (O) _t R ^a reactive group. R ^a , R ^b and R ^c , wherein n and t are groups such as defined above.

  As used herein, the term “heteroatom” means a non-carbon atom such as an oxygen, nitrogen or sulfur atom. If nitrogen atoms are present, they are generally present as part of an amino residue and will be substituted by, for example, hydrogen or alkyl.

The term “amide” generally refers to a group of the formula: C (O) NR ^a R ^b , where R ^a and R ^b are hydrogen or an optionally substituted hydrocarbyl group. It is understood. Similarly, the term “sulfonamide” refers to a group of the formula S (O) ₂ NR ^a R ^b . Suitable R ^a groups include hydrogen or methyl, especially hydrogen.

  The nature of the group attached to the electron withdrawing group or amine moiety used in a particular case depends not only on the nature of other functional groups in the compound but also on the position relative to the double bond that needs to be activated. Also depends. The term “electron withdrawing group” includes within its scope, for example, substituents of atoms such as halo, such as fluoro, chloro, bromo, as well as molecules such as acyl, nitro, carbonyl, etc. Substituents are also included.

For the group of formula (I), X ¹ and Y ¹ , if any, are preferably CX ² X ³ and CY ² Y ³ respectively, and there is no dotted bond.

Preferably, if present, R ¹³ and R ¹⁴ are alkyl groups, more preferably C ₁ -C ₃ alkyl groups.

Advantageously, if present, R ^c is a carbonyl group or a phenyl group substituted in the ortho and / or para position by an electron withdrawing group such as nitro.

When R ¹ is CH═CHR ^d NR ¹⁶ —, R ^d is a carbonyl group or a phenyl group substituted at the ortho and / or para position by an electron withdrawing group such as nitro.

Suitably R ⁷ and R ⁸ are each independently selected from fluoro, chloro or alkyl or H. In the case of alkyl, methyl is most preferred.

Suitably X ² , X ³ , Y ² and Y ³ are all halogen.

At least one, if possible, all of X ² , X ³ , Y ² and Y ³ can be a substituent other than hydrogen or fluorine. Suitably, at least one, and possibly all, X ² , X ³ , Y ² and Y ³ are optionally substituted hydrocarbyl groups. In such embodiments, at least one, and possibly all, X ² , X ³ , Y ² and Y ³ are optionally substituted alkyl groups. Particularly preferred examples _are alkyl groups of C 1 -C _4, particularly, methyl or ethyl. In embodiments where X ² , X ³ , Y ² and Y ³ are alkyl groups, they can polymerize when exposed to radiation without the presence of an initiator. Instead, at least one, preferably all, X ² , X ³ , Y ² and Y ³ are aryl and / or heterocyclic groups such as pyridyl, pyrimidinyl or groups comprising pyridine or pyrimidine.

In a preferred embodiment, R ¹² is
X ¹ and Y ¹ are a CX ² X ³ group and a CY ² Y ³ group, respectively, and the dotted line indicates the absence of a bond. In these embodiments, the polymerization may be performed by cyclopolymerization.

Suitable groups of the polymer precursor used in the method of the present invention are represented by the following formula (II)
And especially the following formula (IIA)
Wherein r is an integer of 1 or more and R ⁶ represents one or more bridging groups, optionally substituted hydrocarbyl groups, perhaloalkyl groups, siloxane groups, amides or repeating units. (Including partially polymerized chain)
It is this compound.

  Preferably, r is 1, 2, 3 or 4.

In preferred embodiments of formula (II), R ¹ is S (O) ₂ N or C (O) N. Therefore, the polymer precursor has the structure (III)
(Wherein R ¹⁵ is C (O) or S (O) ₂ )
It is this compound.

Advantageously, the polymer precursor has the structure (IV)
It is this compound.

In the compounds of formulas (II) to (IV), when r is 1, the compound readily polymerizes and can form various polymer types depending on the nature of the R ⁶ group.

In the compounds of formulas (II) to (IV), when r is greater than 1, a polymer network can be formed by polymerization. During the polymerization of these compounds, a network is formed, the properties of which can be selected depending on the fine nature of the R ⁶ group, the amount of chain terminator present and the polymerization conditions used. . Some examples of bridging groups can be found in WO 00/06610.

Suitably, R ⁶ is a straight or branched hydrocarbyl, optionally intervened by a cyclic group. Advantageously, the linear or branched hydrocarbyl is intervened or substituted with one or more of an amine moiety, C (O) or COOH.

In some embodiments, the polymer precursor is a monomer wherein R ⁶ is a linear or branched hydrocarbyl, or a prepolymer obtained by semi-polymerization of said monomer, mediated by an amine moiety. Suitably, the monomer is a linear or branched alkyl group having 1 to 30 carbon atoms, optionally intervened with a cyclic group. In particular, in a preferred embodiment, the monomer has the formula (V)
(Wherein R ¹⁶ is H or C _s H _{2s + 1} , p is 1 to 10, q is 0 to 10, and s is 1 to 10)
It is this compound.

In another preferred embodiment, the monomer has the formula (VI)
(Wherein t and u are each independently 1 to 10, R ¹⁶ is H or C _s H _{2s + 1} , where s is 1 to 10)
It is this compound.

In other preferred embodiments, the polymer precursor is a monomer where R ⁶ is a linear or branched hydrocarbyl substituted with a COOH end group, or a prepolymer obtained by monomer semi-polymerization. A monomer is a linear or branched alkyl group having 1 to 30 carbon atoms, optionally intervening with a cyclic group. Advantageously, the monomer has the following formula (VII)
(Wherein v is 1 to 20)
It is this compound.

In an alternative embodiment, the polymer precursor is a monomer wherein R ⁶ is a linear or branched alkyl group having 1 to 30 carbon atoms, or a prepolymer obtained by monomer semi-polymerization. .

In yet other embodiments, the polymer precursor is a R ⁶ is a linear or branched alkyl group having 1 to 30 carbon atoms, partially or excessively halogenated, or of the monomer. It is a monomer that is a prepolymer obtained by semi-polymerization. Preferably the alkyl group is a perhalide. Preferably, the alkyl group is fluorinated, more preferably perfluorinated.

In still other embodiments, the polymer precursor is R ¹⁵ is CO and R ⁶ terminates with one or more amine moieties to form a urea structure or It is a monomer that is a prepolymer obtained by semi-polymerization.

In still other embodiments, the polymer precursor has the structure (VIII)
Wherein R ⁶ is a linear or branched hydrocarbyl group, optionally intervened by a group, where r is an integer greater than or equal to 2 or half of the monomers (It is a prepolymer obtained by polymerization)
Monomer. Preferably, r is 2 or 3.

In other embodiments, R ¹⁵ is hydrogen or hydrocarbyl, so that the compound of formula (I) has the formula
Does not contain In these embodiments, a suitable class of compounds of formula (I) has the structure (X)
Wherein R ¹⁶ is only hydrogen, halo, nitro or hydrocarbyl, optionally substituted or mediated by a group.
It is represented by Particularly preferred compounds of formula (X) are those of formula (XI)
It is this compound.

  The entire contents of which are incorporated herein by reference, WO 00/06610, WO 00/06533, WO 00/06658, WO 01/36510, WO 01/40874 and WO 01/74919 have one or more dienyl groups. Disclosed are classes of polymers obtained by polymerization of a number of compounds.

A homopolymer can be obtained by polymerizing the polymer precursor. Alternatively, the copolymer can be obtained by mixing the polymer precursor with one or more other polymer precursors and polymerizing the polymer precursor. Other polymer precursors can be according to any of the formulas described herein. Alternatively, the comonomer can be a different class of compound. The polymer precursor can be copolymerized with a crosslinker. In these embodiments, the polymer precursor has the formula (XII)
Wherein R ¹ , R ² , R ⁴ , R ¹² and X ¹ are as defined for formula (I), r is an integer greater than or equal to 2 and R ⁶ is the valence r Is a cross-linking group or bond of
It can be made to react with this compound.

Preferably r is 2. The polymer precursor is
It is particularly preferred to use a compound of the formula (XII) when the group of However, the following formula
Embodiments of polymer precursors containing groups of can also be reacted with a compound of formula (XII).

The compound of formula (XII) is represented by the following formula (XIII)
It can be set as this compound.

  The monomer or comonomer can be semi-polymerized to obtain a prepolymer. In general, a thermal initiator is used, and the semi-polymerization is performed under a temperature rising condition of room temperature or higher.

  In one class of preferred embodiments, the low surface energy substrate is a low surface energy plastic substrate. Preferably, the low surface energy plastic material is a polyolefin, polyester, polystyrene, styrene copolymer, polyvinyl chloride or a mixture of polyolefin and elastomer. Non-limiting examples of low surface energy plastic substrates are polypropylene, polyethylene, polyethylene terephthalate (PET), polybutadiene terephthalate (PBT), or acrylonitrile-butadiene-styrene.

  The low surface energy plastic substrate is an elastomer. For the avoidance of doubt, the term “elastomer” is meant to refer to natural and synthetic rubber. The coating is conventionally difficult to adhere, such as thermoplastic rubbers such as silicone rubber, fluoro-silicone rubber, fluorocarbon rubber, ethylene propylene rubber including EPDM rubber, styrene-butadiene rubber, nitrile butadiene rubber or styrene-butadiene block copolymer Can be performed on the elastomer.

  In another suitable class of embodiments, the low surface energy substrate is a low surface energy metal such as aluminum, tin, or chromium.

Generally, a low surface energy substrate has a surface energy of 42 mJ / m ² or less.

  Particularly advantageously, the polymer coatings of the present invention can be used as adhesion enhancers in a wide range of useful coatings. In one embodiment, step b) contacts a further substrate with the polymer precursor or the polymerized polymer precursor, wherein step b) comprises that the polymer coating comprises the low surface energy group. In the method of the present invention, comprising the step of joining the material to a further substrate, a composite structure is formed. The further substrate can be a woven fabric. Alternatively, the additional substrate can be any other low surface energy substrate of any type described herein.

  Step b) is carried out by (ii) polymerizing the polymer precursor and contacting the polymer precursor with the low surface energy substrate to form a polymer coating on the low surface energy substrate. Wherein a composite structure is formed comprising a first substrate, the low surface energy substrate, and the polymerized polymer precursor, the polymerized polymer precursor comprising the additional substrate and the low surface The polymer precursor is polymerized on the further substrate to intervene between the energy substrate and bond the two substrates, after which the polymerized polymer precursor is Can be made by contacting with the low surface energy base material while adhering. There are a number of ways in which this can be achieved. In one embodiment, the polymerized polymer precursor is reduced by contacting the polymerized polymer precursor with the polymerized polymer precursor and optionally applying heat and / or pressure. Contact with a surface energy substrate. Alternatively, the polymerized polymer precursor can be contacted with the low surface energy substrate by contacting a molten low surface energy substrate with the polymerized polymer precursor.

  In embodiments where a composite structure is formed by contacting a further substrate with a polymer precursor or polymerized polymer precursor, the polymerized polymer precursor is an elastomer. The further substrate can be a metal or an elastomer.

  Advantageously, the method further comprises a step (c) of applying a further coating to the polymer coating. Advantageously, the polymers obtained according to the invention allow both the coating of low surface energy substrates and the indication of further coatings. While not wishing to be bound by any particular theory, advantageously, at least some of the polymer precursors and polymers used in the present invention allow bonding to a low surface energy substrate to occur. It is believed that it has sufficient hydrophobicity, and if necessary, sufficient hydrophilicity to allow the polymer coating to be well coated with a material having a higher surface energy.

  At least part of the problem with bonding to low surface energy substrates is that the deposited layer must first have a surface tension that is lower than the surface energy surface tension of the substrate. It is sufficiently hydrophobic in nature or otherwise suitable for adhering to low surface energy substrates, but nevertheless double bonds or bonds are sufficiently active with respect to possible polymerization A compound of formula (I) can be provided which can be

  Advantageously, the coating applied to the polymer coating is an adhesive. Thus, the adhesive and polymer coating can cause the structure to adhere to the low surface energy substrate. The structure that is bonded to the low surface energy substrate can be any suitable shape or material. One skilled in the art can select an adhesive according to the nature of the structure to be bonded. In a preferred embodiment, the adhesive is a water based adhesive or a hot melt adhesive. The hot melt adhesive can be formed from a polymeric material. A hot-melt adhesive of polyurethane, polyethylene, polypropylene, or polyethylene terephthalate can be used.

In the second embodiment of the present invention, the following formula (IX)
Wherein R ² , R ³ , R ⁴ , R ⁵ , X ¹ and Y ¹ are as previously defined, and R ¹⁷ is a C ^{3 to} C ¹² alkyl group, preferably C ⁵ to C ⁸ alkyl group, more preferably octyl)
A monomer compound is provided.

  In a third embodiment of the present invention there is provided a polymer obtained by polymerization of a monomer compound of formula (IX) as defined in the second embodiment, or a prepolymer obtained by semi-polymerization of the monomer. The coated substrate can be prepared using either step (i) or step (ii) as defined above.

  In a fourth embodiment of the invention, the coating is a coated coating, which is a polymer coating formed by polymerizing a polymer precursor comprising a group of formula (I) as defined in the first embodiment. Low surface energy substrate.

  The coated low surface energy substrate can include a further coating applied to the polymer coating. The further coating can be a paint, ink, protective coating or adhesive. In embodiments where the outer coating is an adhesive, the coated low surface energy substrate may further comprise a structure adhered to the low surface energy substrate by the adhesive and the polymer coating.

  In a fifth embodiment of the present invention, a low surface energy substrate, a further substrate, and a polymer precursor comprising a group of formula (I) as defined in the first embodiment are bonded together. Provided is a composite structure comprising a low surface energy substrate and a further substrate interlayer formed by polymerization. The composite structure can be prepared using either step (i) or step (ii) as defined above.

  However, any aspect of the present invention described above provides that the low surface energy substrate coated with the polymer coating, having a low surface energy substrate and a further intermediate layer of the substrate, does not include a lip portion of the sealing system. including.

  Although the present invention has been described above, the present invention extends to any invention by combining the partial combinations of the features described above or in the specification, drawings or claims.

Embodiments of a method for coating monomer, polymer, and polyolefin substrates are described with reference to the accompanying drawings.
It is a figure which shows a 1st reaction scheme. It is a figure which shows a 2nd reaction scheme.

Example 1
The target molecule 1 (hexanoic acid (bis (3-methyl-2-butenyl) amide) is shown below.
A synthesis scheme is shown in FIG.

The synthesis of monomer 1 is described below. Reactions 1.1, 1.2, 1.3, and 1.4 were dried solvents; t-butyl methyl ether was dried overnight with CaSO ₄ , passed through alumina, then distilled, and pyridine was (Linde) type 4A molecular sieves, dried and then distilled, tetrahydrofuran (THF) was refluxed with sodium-benzophenone mixture and then collected under an argon atmosphere.

  Column chromatography was performed using flash grade silica.

1.1 Synthesis of 1-bromo-3-methyl-2-butene (2) t-butyl methyl ether (1000 mL) and 3-methylbuten-3-ol (230 g, 280 mL, 2.67 mol) were added to a stir bar, To a multi-necked flask (3 L) equipped with a condenser, thermometer, and dropping funnel. Pyridine (21 g, 22 mL, 0.267 mol) is added and the contents of the flask are stirred at room temperature for 30 minutes, after which PBr ₃ (361 g, 125 mL, 1.33 mol) is added via an addition funnel to the internal temperature. Was added with stirring at a rate that could be maintained below 40 ° C, preferably about 30 ° C (note that the reaction is exothermic). After the addition was complete, the reaction mixture was allowed to stir for 4 hours. TLC and HPLC then showed that the reaction was complete. After returning to room temperature, the mixture was quenched by adding saturated aqueous NaCl (1 L) with stirring bar.

The organic layer was separated and the aqueous layer was extracted with t-butyl methyl ether (3 × 300 mL). The combined organic layers were washed twice with saturated aqueous NaHCO ₃ (2 × 500 mL) and then with saturated brine (2 × 200 mL). The ether layer was dried over anhydrous MgSO ₄ and the solvent was removed under normal pressure. The distillation apparatus was connected to a suction pump (water thickness pump), and the bromide was distilled at 40-60 ° C. under a pressure of about 25 mmHg to obtain a pale yellow oil (318 g, yield: 80%).

1.2 Preparation of tertiary amine (3) A multi-necked flask (2 L) equipped with a stir bar, a condenser, a thermometer, and a dropping funnel was placed in a cooling bath (ice-water), acetone (500 mL), Concentrated aqueous ammonia (30 mL) and anhydrous potassium carbonate (159 g, 1.15 mol) were added. The mixture was stirred at room temperature for 30 minutes. Allyl bromide (52.5 g, 0.35 mol) was added via a dropping funnel over a period of 20 minutes at such a rate that the internal reaction could be maintained below 25 ° C. The reaction solution was stirred at room temperature for 3 hours, after which TLC (silica, DCM with 5% methanol) showed that the reaction was complete. The solid suspension was filtered and washed with acetone (2 × 50 mL). The solvent was removed under reduced pressure to give tertiary amine 3 as a pale yellow product. It then solidified (28 g, crude yield: 107%).

1.3 Preparation of Secondary Amine (4) The crude tertiary amine (9 g, 41 mmol) was added to a 25 mL round bottom (RB) flask equipped with a condenser. The contents of the flask were heated to 200 ° C. over 30 minutes (at external temperature) in DrySyn (RTM) (aluminum block) placed on a stirring hotplate. The solid material began to dissolve at about 140-150 ° C. This material was heated at 200 ° C. for 2.5 hours. The progress of the reaction was monitored by TLC (silica, DCM containing 5% methanol solution of 10% methanol, ammonia). The reaction mixture was then cooled to room temperature.

1.4 Hexanoic acid (bis (3-methyl-2-butene) amide The reaction mixture cooled in the previous step was transferred to a 100 mL RB flask containing potassium carbonate (6 g, 43 mmol) and 30 mL acetone. Stir at room temperature and hexanoyl chloride (3.8 g, 3 mL, 28 mmol) was added dropwise via a dropping funnel over 10 minutes with stirring The reaction mixture was stirred overnight at room temperature and the next day, TLC. (Silica plate, DCM containing 2.5% methanol) showed formation of the desired monomer 1. The solvent was removed under reduced pressure and the solid was washed with 30 mL petroleum ether (40-60) and filtered. Decolorizing charcoal (1 g) was added to the road station, heated to boiling, then filtered hot, and the solvent was removed under reduced pressure to remove a light brown oil (5.0 g, yield: 49 ) Was obtained .HPLC showed a purity of 94%.

(Example 2)
Polymerization of hexanoic acid (bis (3-methyl-2-butenyl) amide (1) Hexanoic acid (bis (3-methyl-2-butenyl) amide (1) was applied to a polypropylene substrate and about 1.5 wt. % Of Irgacure 184 photoinitiator was used to polymerize simply under UV irradiation (mercury discharge UV emitter), and an exposure time of only 1 second was sufficient to cause polymerization.

Example 3
Polymerization of hexanoic acid (bis (3-methyl-2-butenyl) amide (1) without using a photoinitiator Hexanoic acid (bis (3-methyl-2-butenyl) amide (1) was used with a photoinitiator. And polymerized on polypropylene under UV irradiation (mercury discharge UV emitter), curing occurred in just 1 second, and the polymerization was similar in further experiments using a UV light source of an LED operated at 390 nm. The monomer was cured in the absence of photoinitiator.

Example 4
The target molecule 5 (hexanoic acid (bis (3-methyl-2-butenyl) amide) is shown below.
A synthesis scheme is shown in FIG.

4.1 Synthesis of 1-bromo-3-methyl-2-butene (6) 3-Methyl-buten-3-ol (97%, 500 mL) in hydrobromic acid (48%, 1 L) at room temperature, It was added over 2 hours while stirring at a constant speed. The mixture was then allowed to sit for another 2 hours, after which the clear yellow upper layer was decanted away from the water / HBr lower layer. The upper layer was completely dried with CaSO ₄ and then distilled at 63 ° C. to obtain a colorless liquid having a density of 1.26 g / mL.

4.2 Preparation of primary amine (7) Bromomethylbutane 6 was dissolved in acetone (50 mL) and this solution was pre-cooled to −5 ° C. in the presence of potassium carbonate (22 g) with stirring. To a concentrated aqueous ammonium hydroxide solution (25 mL). The mixture was stirred at this temperature for 30 minutes and then allowed to warm to room temperature. This solution and primary amine 7 were removed under reduced pressure.

4.3 Preparation of hexanoic acid (3-methyl-2-butenyl) amide (5) Hexanoyl chloride (3.8 g) is stirred into the secondary amine and acetone at room temperature for 30 minutes with stirring. Added dropwise. The reaction was stirred for 4 hours, after which the solvent was removed under reduced pressure to give a yellow oil. The oil was purified by flash column chromatography on silica gel using dichloromethane as solvent. The target monomer 5 was a pale yellow oil.

(Example 6) Polymerization of hexanoic acid (3-methyl-2-butenyl) amide (5) using a crosslinker Monomer 5 was prepared according to Example 4 and copolymerized with a crosslinker compound.
Example except that the crosslinker compound was replaced with oxaloyl chloride (ClOOCCOOCl) in a molar ratio of 2: 1 (primary amine 7: oxaloyl chloride) used in step 4.3. 4 was prepared using the method described in 4. The crosslinker (5%) was dissolved in monomer 5 (95%) at room temperature and the resulting solution was conveniently copolymerized using the polymerization conditions described in Example 2.

(Example 7)
The target molecule 8 (hexanoic acid diallylamide) is shown below.
Fresh, dried hexanoyl chloride (200 mmol) was placed in a 3-neck round bottom (RB) flask to which 200 mL of dry dichloromethane was added. Freshly dried diallylamine (220 mmol) was added to triethylamine (220 nmol) and further diluted in dry dichloromethane (1: 1 v / v), then added to the addition funnel and mounted on the reaction flask. Nitrogen gas was passed through the container through the other two ports. To neutralize the resulting HCl, the exhaust gas was bubbled through a CaCO ₃ solution. The reaction vessel was then placed in a brine / ice bath and the contents cooled before diallylamine / triethylamine / DCM was added dropwise to the acid chloride solution while the mixture was continuously magnetically stirred. The temperature was monitored and maintained at 5-10 ° C. The dropwise addition of diallylamine and triethylamine was stopped after 3 hours and the reaction was allowed to stir for an additional hour.

  The reaction was monitored using thin layer chromatography with ethyl acetate and alumina, comparing the starting material to the product. The plate was developed using iodine and the reaction product was visualized as a better dissolved spot than the starting material.

  In order to remove ammonium chloride and excess diallylamine, the reaction solution was washed with 3M HCl. Monomer remaining in the DCM fraction was removed using a separatory funnel. For 20 g monomer in 200 mL DCM, 100 mL HCl was washed twice. The solvent was then removed on a rotary evaporator.

  The product was added to dichloromethane (1: 1 v / v) and passed through a silica gel (Merck, chromatographic grade 60) column using dichloromethane as the eluent. Some yellow coloration remained on the column and a very pale yellow oil was obtained after removal of the eluent. The product hexanoic acid (8) was produced in a yield of ˜70%.

(Example 8)
Polymerization of hexanoic acid diallylamide (8) Hexanoic acid diallylamide (8) was applied to a polypropylene substrate, and polymerized simply under UV irradiation using about 1.5% by weight of Irgacure 250 photoinitiator.

Example 9
Polymerization of hexanoic acid diallylamide (8) without the use of a photoinitiator Hexanoic acid diallylamide (8) is applied to a polypropylene substrate, and without using a photoinitiator, relatively strong UV irradiation by a high intensity Fusion UV lamp Polymerized below.

(Example 10)
Polymerization of hexanoic acid diallylamide (8) and crosslinker Monomer 8 was produced according to Example 7 and was a crosslinker compound, N, N, N ′, N′-tetraallylethanediamide (formula below)
And copolymerized.

  The crosslinker compound was prepared using the method described in Example 7 except that hexanoyl chloride was replaced with oxaloyl chloride (ClOOCCOOCl) in a 2: 1 molar ratio (diallylamine: oxaloyl chloride). The crosslinker (5%) was dissolved in monomer 8 (95%) at room temperature and the resulting solution was conveniently copolymerized using the polymerization conditions described in Example 8.

(Example 11)
The target compound 9 (octyl (diallylsulfonamide)) is shown below.

Fresh, dried octylsulfonyl chloride (200 mmol) was placed in a 3-neck round bottom (RB) flask to which 200 mL of dry dichloromethane was added. Freshly dried diallylamine (220 mmol) was added to triethylamine (220 nmol) and further diluted (1: 1 v / v) in dry dichloromethane, then added to the addition funnel and mounted on the reaction flask. Nitrogen gas was passed through the container through the other two ports. To neutralize the resulting HCl, the exhaust gas was bubbled through a CaCO ₃ solution. The reaction vessel was then placed in a brine / ice bath and the contents cooled before diallylamine / triethylamine / DCM was added dropwise to the acid chloride solution while the mixture was continuously magnetically stirred. The temperature was monitored and maintained at 5-10 ° C. The dropwise addition of diallylamine and triethylamine was stopped after 3 hours and the reaction was allowed to stir for an additional hour.

  The reaction was monitored using thin layer chromatography with ethyl acetate and ammonia, comparing the starting material to the product. The plate was developed using iodine and the reaction product was visualized as a better dissolved spot than the starting material.

  In order to remove ammonium chloride and excess diallylamine, the reaction solution was washed with 3M HCl. Monitoring was performed in the DCM fraction and removed using a separatory funnel. For 20 g monomer in 200 mL DCM, 100 mL HCl was washed twice. The solvent was then removed on a rotary evaporator.

  The product was added to dichloromethane (1: 1 v / v) and passed through a silica gel (Merck, chromatographic grade 60) column using dichloromethane as the eluent. The components were then removed to give product (9).

(Example 12)
Polymerization of Octyl (diallylsulfonamide) (9) Octyl (diallylsulfonamide) (9) was polymerized on polypropylene under the conditions described in Example 2.

(Example 13)
Improved adhesion of SBR rubber to aqueous adhesives using copolymers of N, N-diallyl-3- (propylamino) propanamide and N, N, N ′, N′-tetraallylethanediamide A mixture of N, N-diallyl-3- (propylamino) propanamide (1060.5 g) and N, N, N ′, N′-tetraarylethanediamide (79.5 g) was heated to 80 ° C. and constant. Maintained at this temperature with rapid stirring. To this mixture was dissolved N, N-diallyl-3- (propylamino) propanamide (264.75 g) and N, N, N ′, N′-tetraallylethanediamide (20.25 g). A concentration of Vazo 67 (Dupont) thermal initiator (75.0 g) was added dropwise over 6 hours with stirring to maintain the reaction temperature at 80 ° C. After the high concentration was added, the reaction was left at room temperature for an additional 12 hours with continuous stirring and then allowed to cool to room temperature to give a viscous brown oil. ITX photoinitiator (45.0 g) and ethyl 4-dimethylaminobenzoate synergist (30.0 g) were then added and completely dissolved in the reaction product.

  A layer of this formulation was coated on a sheet of SBR rubber flooring with a coating weight of about 2 gsm and cured at a belt speed of 4 meters / minute using a 200 W / cm focused UV source with an iron-doped mercury bulb. I let you.

Synthesis of N, N-diallyl-3- (propylamino) propanamide
3-Bromopropynyl chloride (1: 1 v / v) in dichloromethane was added dropwise to diallylamine in a slight molar excess of dichloromethane (DCM) at −10 ° C. over 2 hours with continuous stirring. And added. This was then washed in dilute HCl and DCM and the organic fraction was collected. The DCM solution of the product was then purified by column chromatography using silica (60A) and dichloromethane was removed to give the 3-bromo-N, N-diallylpropylamide intermediate; yellow liquid (density : ˜1.27 g / cm ³ ). Yield 70% +.

  Intermediate from 1 (30 g, 129 mmol) was added to THF (1: 1 v / v). This was then stirred and refluxed into a mixture of 1-propylamine (43.1 g, 0.730 mmol), potassium carbonate (90 g, 0.652 mmol), and THF (133.6 g, 1.850 mmol). Added dropwise over 2 hours. The reflux was then allowed to cool over 1 hour with continuous stirring.

  The cooled reaction mixture was washed with water (400 mL) and potassium carbonate was dissolved to give a clear yellow organic top layer that was decanted. This layer was then washed again with water, separated and dried to give a yellow liquid. Yield: ~ 65%.

(Example 14)
To a cyanoacrylate adhesive using an adhesion enhancing layer composed of a polymer made of 2,2,3,3,4,4,4-heptafluoro-N, N-di (2-propen-1-yl) butanamide , Improvement in adhesion of poly (propylene) / EPDM substrate Photoinitiator Irgacure 184 (Ciba SC) (0.075 g) was added to 2, 2, 3, 3, 4, 4, 4-heptafluoro-N, N -Dissolved in di (2-propen-1-yl) butanamide (2.50 g) and deposited as a thin film on poly (propylene) / EPDM panels using a foam roller. A round piece of mild steel was polished with glass paper and then bonded to a poly (propylene) / EPDM surface coated with a cyanoacrylate adhesive.

Synthesis of 2,2,3,3,4,4,4-heptafluoro-N, N-di (2-propen-1-yl) butanamide N, N-diallylamine (9.50 g, 96. 8 mmol), and dry dichloromethane (50.0 g) was bubbled with nitrogen for 1 h, then transferred to a dropping funnel and sealed. This mixture was then cooled (5 ° C.) of heptafluorobutanoyl chloride (10.0 g, 43 mmol) in dry dichloromethane (100 g) that had been purged with nitrogen with continuous stirring for 1 hour in advance. Was added dropwise over a period of 2 hours. The temperature was maintained at <10 ° C. during the addition of diallylamine solution and for 1 hour thereafter. After this time, the solution was warmed to room temperature and the reaction mixture was washed with water (300 mL). The organic layer was washed twice more with water (300 mL), separated and dried over anhydrous magnesium sulfate. The solvent and volatiles were then removed from the organic layer under reduced pressure to yield a yellow liquid that was further purified using column chromatography using silica and dichloromethane as the eluent. The eluent was then removed under reduced pressure to give a pale yellow liquid. Yield = 62%.

(Example 15)
Poly (urethane) hot melt adhesive and PUR foam laminate for nitrile butadiene rubber (NBR) using an adhesion enhancing layer made of a polymer made of N, N-diallyl-2- (butyl-diallylcarbamoylmethylamino) acetamide N, N-diallyl-2- (butyl-diallylcarbamoylmethylamino) acetamide (890.0 g) is preheated to 80 ° C. and then N, N-diallyl-2- (butyl-diallylcarbamoylmethyl) A mixture of thermal initiator Vazo67 (DuPont) (10.0 g) in (amino) acetamide (100.0 g) was stirred for 2 hours under a nitrogen atmosphere with continuous stirring while maintaining the temperature at 80 ° C. Added over. The reaction was allowed to react for an additional 14 hours under the same conditions and then cooled to room temperature.

  Photoinitiator 2-isopropylthioxanthone (ITX) (31.8 g) and synergist ethyl-4- (dimethylamino) benzoate (EDB) (21.2 g) were then added, before use. It was completely dissolved in the mixture.

  This formulation was then coated on the floor of an NBR rubber flooring using a reverse roller method with a coating weight of 2 grams per square meter and with a 200 W / cm UV lamp using an iron-doped mercury bulb. Cured.

A moisture-curing MDI-based polyurethane hot melt (100% solids) was then deposited at 160 ° C. on NBR with improved adhesion at a coating weight of 70-80 g / m ² . Immediately after, the PUR foam sheet was laminated onto the hot melt coating under pressure and cooled to room temperature.

Synthesis of N, N-diallyl-2- (butyl-diallylcarbamoylmethylamino) acetamide
Chloroacetyl chloride (98%, 212 g, 1.883 mmol) and dichloromethane (397.5 g, 4.680 mmol) were added to the reaction vessel and cooled to 5 ° C. N, N-diallylamine (freshly distilled, 402.57 g, 4.143 mmol) is added to dichloromethane (397.5 g, 4.680 mmol) and the mixture is then continuously stirred to maintain the temperature below 10 ° C. While dropping over several hours, it was added dropwise to the chloroacetyl chloride mixture. The reaction mixture was then left to reach room temperature and then washed with water (1.5 L). The organic layer was washed again with water and then the organic layer was separated. Solvent and volatiles were then removed from the organic layer under reduced pressure to give a yellow oil. This was further purified by column chromatography using ethyl acetate eluent and silica. The eluent was removed under reduced pressure to give a yellow oil. The yield was ˜78%.

  N, N-diallyl-2-chloroacetamide (intermediate) (86.75 g, 0.500 mmol), triethylamine (154.38 g, 1.500 mmol) and tetrahydrofuran (222.25 g, 3.082 mol) were combined with 1-butylamine. (99%, 18.29 g, 0.250 mol) was added dropwise to the reaction flask over 15 minutes with continuous stirring. The reaction temperature was brought to reflux temperature and maintained for 4 hours. The reaction was then cooled to room temperature and then triethylamine hydrochloride was filtered from the reaction. After removing the solvent under reduced pressure, the product was added to dichloromethane (200 mL) and then washed twice with water (300 mL). Satsuki Yuki was separated, dried over magnesium sulfate and filtered. This was removed under reduced pressure to give a pale yellow oil. The yield was ˜88%.

(Example 16)
Improved adhesion of solventless acrylate-dispersed flooring adhesive to styrene-butadiene rubber (SBR) using an adhesion enhancing layer made of a polymer made of N, N-diallyl-2- (butyl-diallylcarbamoylmethylamino) acetamide N, N-diallyl-2- (butyl-diallylcarbamoylmethylamino) acetamide (890.0 g) is preheated to 80 ° C. and then N, N-diallyl-2- (butyl-diallylcarbamoylmethylamino) acetamide (100 A mixture of thermal initiator Vazo67 (DuPont) (10.0 g) in 0.0 g) was added over 2 hours under a nitrogen atmosphere with continuous stirring while maintaining the temperature at 80 ° C. The reaction was allowed to react for an additional 14 hours under the same conditions and then cooled to room temperature. Photoinitiator 2-isopropylthioxanthone (ITX) (31.8 g) and synergist ethyl-4- (dimethylamino) benzoate (EDB) (21.2 g) were then added, before use. It was completely dissolved in the mixture.

  This formulation was then coated on the floor of an SBR rubber flooring using a reverse roller method with a coating weight of 2 grams per square meter and with a 200 W / cm UV lamp using an iron-doped mercury bulb. Cured.

The SBR rubber thus treated was then bonded to a wooden flooring coated with a solventless acrylate dispersion adhesive with a coating weight of 350 g / m ² using a diffusion iron. Approximately 15 minutes were allowed between the spreading of the adhesive and the bonding of the SBR to the rubber with equal force on the SBR surface after the SBR was placed on the wooden flooring.

(Example 17)
N, N-diallyl-3- (propylamino) propanamide and 1,1-diallyl-3- (6- {3,5-bis- [6- (3,3-diallyl-ureido) -hexyl]- 2,4,6-Trioxo- [1,3,5] -triazinan} -1-yl-hexyl) Improved adhesion between NBR rubber and FKM fluoroelastomer using adhesion enhancing layer made of urea Thermal initiator Vazo67 (DuPont) at 5% by weight, N, N-diallyl-3- (propylamino) propanamide and 1,1-diallyl-3- (6- {3,5-bis -[6- (3,3-diallyl-ureido) -hexyl] -2,4,6-trioxo- [1,3,5] -triazinan} -1-yl-hexyl) urea each in 4: 1 In a mixture by weight The added. The mixture was heated to 80 ° C. and maintained for 16 hours under a nitrogen atmosphere with continuous stirring. After the reaction was cooled, the photoinitiators 2-isopropylthioxanthone (ITX) and ethyl-4- (dimethylamino) benzoate (EDB) were added at 3 wt% and 2 wt%, respectively, and completely dissolved in the mixture. Dissolved in.

A thin, uniform layer of this formulation is coated on a piece of vulcanized FKM fluoroelastomer with a coating weight of about 3 g / m ² , followed by 200 W / cm focused UV with an iron-doped mercury bulb. Cured using a source at a belt speed of 4 meters / minute. The strip of vulcanized NBR rubber was then placed on top of the coated FKM fluoroelastomer and heated at 180 ° C. and a pressure of about 4 bar for 10 minutes.

1,1-diallyl-3- (6- {3,5-bis- [6- (3,3-diallyl-ureido) -hexyl] -2,4,6-trioxo- [1,3,5]- Triazinan} -1-yl-hexyl) urea

1,1-diallyl-3- (6- {3,5-bis- [6- (3,3-diallyl-ureido) -hexyl] -2,4,6-trioxo- [1,3,5]- Synthesis of triazinane-1-yl-hexyl) urea N, N-diallylamine (freshly dried, 30.60 g) was added to an isocyanate “Tolonate HDT-LV2” in dichloromethane (> 99.5%, 132.50 g). ) "(Rhodia) (50.4 g) was added dropwise over a period of 2 hours with continuous stirring while maintaining the temperature below 30 ° C. After the diallylamine was added, the mixture was left for another 30 minutes at room temperature. The solvent and excess diallylamine were removed under reduced pressure to give a highly viscous, amber liquid in 80.1% yield.

(Example 18)
Improvement of adhesion of cyanoacrylate adhesive to poly (propylene) using N, N-di (2-propylene-1-yl) octane-1-sulfonamide N, N-di (2-propylene-1) A formulation comprising Ciba Irgacure 184, (1.5 wt%), and Dupont Vazo 67 (2 wt%) dissolved in -yl) octane-1-sulfonamide It was adjusted.

  A thin film of this formulation, about 5 microns thick, was coated on poly (propylene) plaques and cured using a 160 W / cm focused UV source with an undoped mercury bulb. This process was repeated to form a bilayer on poly (propylene).

  The two pieces of poly (propylene) with improved adhesion in this way were then bonded together using a cyanoacrylate adhesive.

N, N-di (2-propylene-1-yl) octane-1-sulfonamide

Synthesis of N, N-di (2-propylene-1-yl) octane-1-sulfonamide Diallylamine (99%, 10.69 g), triethylamine (99%, 11.1 g), and dichloromethane (99 +%, 50 mL) Were added dropwise to a cooled (0 ° C.) mixture of 1-octane-1-sulfonyl chloride (99 +%, 21.3 g) in dichloromethane (99 +%, 200 mL). With continuous stirring, all diallylamine mixtures were added while maintaining the temperature at 0-10 ° C for several hours. The reaction mixture was then allowed to reach room temperature.

  The reaction mixture was then washed with dilute HCl (3M, 500 mL) and the organic layer was separated. The washing of the organic layer was repeated with water or brine, and the organic layer was dried over anhydrous magnesium sulfate. Dichloromethane and other filtrates were then removed under reduced pressure to produce a pale yellow liquid. This was then further purified by column chromatography using silica gel (60Å) and dichloromethane as the eluent to give a pale yellow oil.

(Example 19)
Adhesion of polymer made of N, N-diallylhexanamide to metal and improved adhesion of PET to metal Tin plates and steel samples without tin were coated after washing with ethyl acetate. The coating was a mixture of 95% N, N-diallylhexanamide and 5% Irgacure 184 initiator. Prior to application of the coating to the metal substrate, the coating was decompressed with ethyl acetate at a 3: 1 ratio of ethyl acetate: N, N-diallylhexanamide. The coating was applied to each metal sample with an approximately dry film of 1.5 μm thickness. The sample thus coated was then dried in an oven at 100 ° C. for 20 minutes to remove the solvent and optionally initiate the reaction between the monomer and the metal surface with heat. After drying, the coating was cured with a UV lamp. PET was then applied by dissolving in an oven at a temperature of 260 ° C. and allowed to dry for 2 minutes. The coated metal samples were then tested for cross-batch adhesion to BS EN ISO 2409 and flexibility and adhesion after bending at 180 ° C. Excellent wettability and adhesion of the tin plate and the steel material without tin were observed. Complete adhesion to the metal sample was observed, i.e. no peeling of the coating on the plate used in the adhesion test. In addition, complete adhesion to PET was observed and no PET cracking or cracking occurred.

Synthesis of N, N-diallylhexanamide
Diallylamine (99%, 37 g, 381 mmol), triethylamine (99%, 40 g, 396 mmol), and dichloromethane (99 +%, 50 mL) were mixed to give hexanoyl chloride (99 +%, 50 g) in dichloromethane (99 +%, 200 mL). 371 mmol), was added dropwise to the cooled (0 ° C.) mixture. With continuous stirring, all diallylamine mixtures were added while maintaining the temperature at 0-10 ° C for several hours. The reaction mixture was then allowed to reach room temperature.

  The reaction mixture was then washed with dilute HCl (3M, 500 mL) and the organic layer was separated. The washing of the organic layer was repeated with water or brine, and the organic layer was dried over anhydrous magnesium sulfate. Dichloromethane and other filtrates were then removed under reduced pressure to produce a pale yellow liquid. This was then further purified by column chromatography using silica gel (60Å) and dichloromethane as the eluent to give a nearly colorless oil. Yield = 70%.

(Example 20)
Adhesion of polymers made of N, N-diallyl-3- (propylamino) propanamide For the monomer N, N-diallyl-3- (propylamino) propanamide, the method described in Example 19 above was used. . During drying, almost complete wettability of the metal sample was observed, although some mesh was seen in the coating. Adhesion to metal samples was excellent and adhesion to PET was very good.

(Example 21)
Of a polyethylene coating on aluminum using an adhesion enhancing layer consisting of a polymer made of N, N-diallyl-3- (propylamino) propanamide and N, N, N ′, N′-tetraallylethanediamide Improving adhesion The aluminum substrate is made from N, N-diallyl-3- (propylamino) propanamide (70%), N, N, N ′, N′-tetraallylethanediamide (25%), and Irgacure 127. Coated with (5%) mixture. The coating was cured under a UV lamp (Fusion UV F300, 120 W / cm) at a belt speed of 2 to 2.5 m / min and subjected to two “dry” cures in 4 passes. Extruded PE (treated and untreated) was coated on the cured aluminum sample. The adhesion of the polymer coating to aluminum was tested by standard test methods of ISO 4264, EN 24624, and ASTM D 4541 and a good adhesion value of 7.8 MPa was recorded. Good adhesion to the PE coating was also observed and a “T-type” adhesion value of 2.0 N / 15 mm was recorded.

(Example 22)
Improved adhesion of water-based paints to polypropylene and high-density polyethylene using an adhesion-enhancing layer consisting of a polymer made of N, N-diallylhexanamide Polypropylene (PP) and high-density polyethylene (HDPE) panels to 2-propanol Washed by wiping with. This panel was then treated with 90.2 wt% N, N-diallylhexanamide, 2.3 wt% 1,3,5-trimesoylamide crosslinker (benzene-1,3,5-tricarboxylic acid-tris- N, N-diallylamide), 4.5 wt% Speedcure ITX photoinitiator, 3.0 wt% Speedcure EDB synergist. The coated panel was then passed under a 120 W / cm UV lamp equipped with an iron-doped mercury bulb, resulting in a cured film about 3 μm thick. After cooling the coated panels, paint (Senosol Hydrometallic (RTM), Welburger Coatings GmbH, D-35781, Welburger-Lahn, Germany) was applied and dried according to the manufacturer's specifications. The adhesion of the polymer coating to PP and HDPE panels and paint was determined according to ASTM D3359B / BS EN ISO 2409. In both cases, 5B, an excellent ASTM D3359B adhesive rating, was obtained.

Benzene-1,3,5-tricarboxylic acid-tris-N, N-diallylamide

Synthesis of benzene-1,3,5-tricarboxylic acid-tris-N, N-diallylamide A mixture of N, N-diallylamine (128.26 g, 1.32 mmol) and dichloromethane (106.0 g, 1.248 mmol) In a reaction vessel containing a cooled (10 ° C.) mixture of benzene-1,3,5-trimesoyl chloride (53.1 g, 0.200 mmol) in dichloromethane (530.0 g, 6.24 mmol) in addition to the funnel. The solution was added dropwise over 75 minutes with continuous stirring. The temperature was maintained at <10 ° C. during the addition of the diallylamine solution and then allowed to return to room temperature over a further 60 minutes with continuous stirring. The organic layer was washed with excess water (1 × 600 mL and 2 × 300 mL) to remove diallylamine hydrochloride and then dried over anhydrous magnesium sulfate. The solid was then filtered and the solvent removed under reduced pressure. The crude product was then purified using column chromatography with silica and dichloromethane as eluent. Dichloromethane was then removed again under reduced pressure to give a pale yellow viscous product. Yield = 60.2%.

(Example 23)
Improved adhesion of m-aramid to silicon and fluoroelastomers using N, N-diallylhexaneamide and N, N, N ′, N′-tetraallylethanediamide N, N-diallylhexaneamide, and Add N, N, N ′, N′-tetraallylethanediamide mixture (9: 1 weight ratio), thermal initiator (Vazo67, Dupont, 5% by weight of monomer mixture) until completely dissolved Stir. This mixture was then maintained at 70 ° C. for 8 hours with continuous stirring to give a viscous yellow oil. To this was added a photoinitiator (Ciba, Irgacure 819, 2 wt%) and mixed well.

  This formulation was then applied at a coating weight of about 5 grams per square meter on each side of a strip of m-aramid fabric (Dupont, Nomex). The coating was cured using a 200 W / cm UV source with an iron-doped mercury bulb continuously after each layer was deposited.

  A fluoro-elastomer strip and silicon compound containing an initiator, or other curing agent, is applied to each side of the woven fabric with increased adhesion and then treated at 190 ° C., 65-80 psi for about 15 minutes. The fluoroelastomer and silicone rubber were cured and bonded to the woven fabric.

N, N, N ′, N′-tetraallylethanediamide

(Example 24)
Improved adhesion of m-aramid to EPDM rubber using N, N-diallyl-3- (propylamino) propanamide and N, N, N ′, N′-tetraallylethanediamide m-aramid fabric A coating method of the same formulation as used in Example 23 was used for the m-aramid fabric except that was placed between the two EPDM rubber compounds. The m-aramid fabric was bonded to EPDM for 15 minutes under high pressure (45-75 psi) and temperature (190 ° C.).

(Example 25)
Benzene-1,3,5-tricarboxylic acid-tris-N, N-diallylamide and 2,2,2 ′, 2 ″, 2 ′ ″-(ethane-1,2-diylbis (azanetriyl) tetrakis ( Improved adhesion of m-aramid to silicon and fluoroelastomer using N, N-diallylacetamide) Benzene-1,3,5-tricarboxylic acid-tris-N, N-diallylamide, and 2,2, Mixtures of 2 ′, 2 ″, 2 ′ ″-(ethane-1,2-diylbis (azanetriyl) tetrakis (N, N-diallylacetamide) were each prepared at a weight ratio of 9: 1. (Ciba, Irgacure 127) was dissolved by adding 3% of the total weight of the monomer mixture and maintaining gentle heating of the mixture. After that, on each side of a strip of m-aramid fabric (Dupont, Nomex), with a coating weight of about 10 grams per square meter, this coating was applied after each layer was deposited. Continuously cured using a 200 W / cm UV source with an iron doped mercury bulb.

  Fluoro-elastomer strips and silicon compounds containing initiators or other curing agents are applied to each side of the woven fabric with increased adhesion and then treated at 175 ° C., 40 ton pressure press for about 25 minutes. The fluoroelastomer and silicone rubber were cured and bonded to the woven fabric.

Benzene-1,3,5-tricarboxylic acid-tris-N, N-diallylamide

Synthesis of benzene-1,3,5-tricarboxylic acid-tris-N, N-diallylamide A mixture of N, N-diallylamine (128.26 g, 1.32 mmol) and dichloromethane (106.0 g, 1.248 mmol) In a reaction vessel containing a cooled (10 ° C.) mixture of benzene-1,3,5-trimesoyl chloride (53.1 g, 0.200 mmol) in dichloromethane (530.0 g, 6.24 mmol) in addition to the funnel. The solution was added dropwise over 75 minutes with continuous stirring. The temperature was maintained at <10 ° C. during the addition of the diallylamine solution and then allowed to return to room temperature over a further 60 minutes with continuous stirring. The organic layer was washed with excess water (1 × 600 mL and 2 × 300 mL) to remove diallylamine hydrochloride and then dried over anhydrous magnesium sulfate. The solid was then filtered and the solvent removed under reduced pressure. The crude product was then purified using column chromatography with silica and dichloromethane as eluent. Dichloromethane was then removed again under reduced pressure to give a pale yellow viscous product. Yield = 60.2%.

2,2 ′, 2 ″, 2 ″ ′-(ethane-1,2-diylbis (azanetriyl) tetrakis (N, N-diallylacetamide)

  A mixture of 4-dimethylaminopyridine (0.5 g), dicyclohexylcarbodiimide (103.0 g), ethylenediaminetetraacetic acid (36.0 g), diallylamine (53.0 g), and dichloromethane (250 g) was added to the reaction vessel and continuously. Maintained at about 20 ° C. for 120 hours with stirring. The urea-containing solid formed in the reaction was then removed by filtration, after which the amine and solvent were removed under reduced pressure. After removal of impurities, a clear viscous oil was obtained (˜65%).

(Example 26)
Improved adhesion of poly (ester) woven fabrics to silicone rubber and fluoroelastomer using N, N-diallylhexaneamide and N, N, N ′, N′-tetraallylethanediamide 9: 1 weight For a mixture of N, N-diallylhexaneamide and N, N, N ′, N′-tetraallylethanediamide in the ratio, the thermal initiator (Vazo 67, DuPont) 1% by weight of the mixture, increased by 1% after each reaction time and added to 5% until the reaction time was 8 hours; the reaction temperature was maintained at 70 ° C. over the entire reaction time. A viscous yellow oil was obtained. To this, a photoinitiator (Ciba, Irgacure 819) was added at 2% by weight of the total solution and mixed well. This formulation is then applied on each side of a strip of knitted poly (ester) woven fabric at a coating weight of about 5 grams per square meter, and after each layer is deposited, UV curing is applied continuously. went.

  A fluoro-elastomer strip and a silicone compound are applied to each side of a knitted poly (ester) woven fabric coated with a layer of enhanced adhesion and then treated at 190 ° C., 45-75 psi for about 25 minutes. The fluoroelastomer and silicone rubber were cured and bonded to the woven fabric.

(Example 27)
N, N-diallylhexaneamide, benzene-1,3,5-tricarboxylic acid-tris-N, N-diallylamide, and fluorinated monomers 2,2,3,4,4,5,5, Poly (aramid) weave for silicone rubber and fluoroelastomer using 6,6,7,7,8,8,8-pentadecafluoro-N, N-di (2-propen-1-yl) octanamide Improvement of fabric adhesion N, N-diallylhexaneamide (85.5% by weight), benzene-1,3,5-tricarboxylic acid-tris-N, N-diallylamide (9.5% by weight), 2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 8-pentadecafluoro-N, N-di (2-propen-1-yl) octaneamide (2 % By weight) and photoinitiator Irgacure 127 (triple) A mixture of% by weight, Ciba SC) was applied on each side of a strip of m-aramid fabric (Dupont, Nomex) at a coating weight of about 10 grams per square meter. The coating was cured using a 200 W / cm UV source with an iron-doped mercury bulb continuously after each layer was deposited.

  Fluoro-elastomer strips and silicon compounds containing initiators or other curing agents are applied to each side of the woven fabric with increased adhesion and then treated at 175 ° C., 40 ton pressure press for about 25 minutes. The fluoroelastomer and silicone rubber were cured and bonded to the woven fabric.

2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-N, N-di (2-propen-1-yl) octaneamide

2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-N, N-di (2-propen-1-yl) octaneamide A mixture of perfluorooctanoyl chloride (20.0 g) and dichloromethane (1.6 g) was added to a stirring mixture of diallylamine (9.88 g,> 99%) and dichloromethane (1.72 g). Add dropwise over time and cool to 0 ° C. The reaction was allowed to warm to room temperature with continuous stirring for an additional hour.

  The product was washed twice with water (500 mL) and then the dichloromethane was removed under reduced pressure to give an orange-yellow liquid with very low viscosity (yield 79%).

Claims (17)

A method of coating a low surface energy plastic substrate;
Formula (I)

Wherein R ¹ is C (O) N, S (O) ₂ N, C (O) ON, or CH ₂ ON;
R ¹² is hydrogen, halo, nitro;
R ² is selected from the group (CR ⁷ R ⁸ ) _n or CR ⁹ R ¹⁰ , CR ⁷ R ⁸ CR ⁹ R ¹⁰ or CR ⁹ R ¹⁰ CR ⁷ R ⁸ , where n is 0, 1 or 2, R ⁷ and R ⁸ are each independently selected from fluoro, chloro, hydrogen or alkyl, either R ⁹ or R ¹⁰ is hydrogen and the other is an electron withdrawing group Or R ⁹ and R ¹⁰ together form an electron withdrawing group;
R ⁴ is selected from CH or CR ¹¹ where CR ¹¹ is an electron withdrawing group;
X ¹ is a CX ² X ³ group, wherein X ² and X ³ are each independently selected from hydrogen, fluorine, or an optionally substituted hydrocarbyl group)
Providing a polymer precursor comprising:
Step a); and
(I) coating the low surface energy plastic substrate with the polymer precursor and polymerizing the polymer precursor to form a polymer coating, or
(Ii) polymerizing the polymer precursor and contacting the polymerized polymer precursor with the low surface energy plastic substrate to form a polymer coating on the low surface energy plastic substrate;
One of the
Step b)
Only including,
The method, wherein the low surface energy plastic substrate has a surface energy of 42 mJ / m ² or less . The polymer precursor has the structure (II)
Wherein r is an integer of 1 or more and R ⁶ represents one or more bridging groups, optionally substituted hydrocarbyl groups, perhaloalkyl groups, siloxane groups, amides or repeating units. (Including partially polymerized chain)
The method according to claim 1, wherein the compound is: The polymer precursor has the structure (III)
(Wherein R ¹⁵ is C (O) or S (O) ₂ )
The method according to claim 2, wherein the compound is: R ⁶ is a linear or branched chain hydrocarbyl group, characterized in that it comprises a substituted or interposed with optionally functional groups The method of claim 2.   5. The method of claim 4, wherein the linear or branched group is intervened or substituted with one or more of an amine moiety, C (O) or COOH. The polymer precursor is a monomer, wherein R ⁶ is a linear or branched hydrocarbyl mediated by an amine moiety, or a prepolymer obtained by semi-polymerization of the monomer. 5. The method according to 5. The polymer precursor is a monomer, wherein R ⁶ is a linear or branched hydrocarbyl substituted with a COOH end group, or a prepolymer obtained by semi-polymerization of the monomer, Item 6. The method according to Item 5. In the polymer precursor, R ⁶ is a linear or branched alkyl group having 1 to 30 carbon atoms, or a partially or excessively halogenated linear or branched alkyl group, or The method according to claim 4, wherein the monomer is a prepolymer obtained by semi-polymerization of a monomer. The polymer precursor is R ¹⁵ is CO and R ⁶ terminates with one or more amine moieties to form a urea structure or a prepolymer obtained by semi-polymerization of the monomers. The method according to claim 3, wherein the monomer is a polymer.   10. The method according to any one of claims 1 to 9, characterized in that the low surface energy plastic substrate is a polyolefin, polyester, polystyrene, styrene copolymer, polyvinyl chloride, or a mixture of polyolefin and elastomer. .   11. The method according to any one of claims 1 to 10, characterized in that the low surface energy plastic substrate is polypropylene, polyethylene, polyethylene terephthalate, polybutylene terephthalate, or acrylonitrile-butadiene-styrene. 2. The low surface energy plastic substrate is silicone rubber, fluoro-silicone rubber, fluorocarbon rubber, ethylene propylene rubber, styrene-butadiene rubber, nitrile butadiene rubber, or styrene-butadiene block copolymer. The method according to any one of to 9 . 請 Motomeko 1 The method according to any one of 12,
Step b) contacts a further substrate with the polymer precursor or the polymerized polymer precursor, wherein step b) further comprises the polymer coating further forming the low surface energy plastic substrate. Performed to bond with a substrate. Applying a further coating to said polymer coating c)
Further comprising the method of any one of claims 1 to 12. 15. A method according to claim 14 , characterized in that the coating applied to the polymer coating is a protective coating or adhesive such as a paint, ink, polyurethane layer or the like. A coated low surface energy plastic substrates, the coating is a polymer coating formed by polymerizing polymer precursors containing a group of the formula (I) according to 請 Motomeko 1,
A surface energy plastic substrate, wherein the low surface energy plastic substrate has a surface energy of 42 mJ / m ² or less . A low surface energy plastic substrate, a further substrate, and a polymer precursor comprising both the low surface energy plastic substrate and the further substrate bonded together and comprising a group of formula (I) according to claim 1 is formed by polymerizing the body, the low surface energy plastic substrates and the intermediate layer of said further substrate, viewed contains a
A composite structure in which the low surface energy plastic substrate has a surface energy of 42 mJ / m ² or less .